GB2150853A - Catalyst for reforming or aromatic hydrocarbon production - Google Patents

Description

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SPECIFICATION

Process for catalytic reforming or aromatic hydrocarbon production

5 The present invention relates to a process for catalytic reforming or aromatic hydrocarbon production in the presence of an alumina catalyst containing an active phase generally comprising at least one metal from Group VIII of the Periodic Table of elements and at least one additional metal used as promoter.

Catalysts have generally been hitherto prepared in two steps:

a) the carrier is prepared or obtained commercially, and 10 b) an active phase is then deposited on the carrier.

The active phase contains generally (a) at least one metal usually from Group VIII of the Periodic Table of elements, generally present in the catalyst as the metal itself or for example as an oxide or sulfide, and ((J) optionally at least one so-called additional metal (or promoter) from any Group of the Periodic Table of elements, generally present in the catalyst as an oxide or sulfide for example.

15 According to the prior art, several methods may be used to incorporate the active phase of the catalyst into the carrier. Generally, each metal individually or all the metals together may be incorporated into the carrier by a suitable method, consisting of co-precipitation or cogelation with the porous carrier, ionic exchange with the gelled carrier, or impregnation of the carrier, either before or after drying and firing the latter.

We now provide a process for the manufacture of a catalyst comprising an active phase consisting of at 20 least one metal of the platinum family and at least one additional metal, and a carrier obtained by admixture of a binding agent with a charge, the process comprising the following steps:

1) admixture of the charge, the binding agent and at least a portion of the active phase,

2) shaping the mixture,

3) drying and optionally firing, and

25 4) optional introduction of the remaining portion of the active phase, followed by drying and then activation.

In this process, the major part of the metals of the platinum family and/or the major part of the additional metals are introduced either with the binding agent or with the charge during the first step.

In the present invention, the catalyst carrier is prepared from an aqueous alumina composition. The carrier 30 comprises the binding agent, generally constituting a dispersed part, and a charge, generally constituting a non-dispersed part of the composition. Preferably, the dispersion ratio of the composition in water, resulting from the admixture of the binding agent with the charge, ranges from about 10 to 60%. For certain uses of the catalysts, the particle size of the non-dispersed part of the composition may be further so selected that the average diameter of the alumina particles of which it is formed ranges from 1 to 15 microns, at least 70% 35 of said particles having an average diameter between half the average diameter and twice said average diameter.

The dispersion ratio is represented by the proportion of alumina remaining in total colloidal suspension after the composition has been subjected to centrifugation. This dispersion ratio may be measured as follows: the aqueous alumina composition is diluted so as to give a total alumina concentration of 100 g/l; 40 100 cc of said solution are subjected to vigorous stirring for 10 minutes; the solution is then centrifuged for 10 minutes at 3000 r.p.m; and the settled part is separated from the unsettled part formed of alumina colloidal suspension. After firing, the settled part is weighed, and the dispersion ratio is expressed as the ratio between the initial total amount of alumina composition less the settled alumina amount, in proportion to the total initial alumina amount of the composition.

45 According to the present invention, the dispersion ratio in water of the aqueous alumina composition is preferably 10-100%, more particularly 15-40%, the particle size of the non-dispersed part of the composition is such that the average diameter of the alumina particles of which it is formed ranges preferably from 1 to 15 microns.

The non-dispersed part of the composition generally consists of the charge; but a minor fraction thereof 50 may come from the binding agent.

The proportion of binding agent in the composition is preferably 10-60% and more particularly 15-40% referred to the total weight of carrier. Accordingly, the weight proportion of the charge in the composition is 40-90%; more particularly 60-85%.

According to the invention, the alumina binding agent generally comprises a portion of dispersed alumina 55 and optionally a minor portion of non-dispersed alumina, the dispersed portion amount preferably to at least 70% by weight of the binding agent. Hereinafter, the term "binding agent" will be used to designate the dispersed portion (even if all the binding agent is not dispersed) and the term "charge" will designate the non-dispersed portion (even if a portion of the charge, smaller than 10% by weight, is in a dispersed state).

The invention provides a process for catalytic reforming or aromatic hydrocarbon production, in the 60 presence of a catalyst comprising (a) a carrier, a major part of which is formed of alumina, and (b) an active phase, the alumina carrier used for the manufacture of the catalyst being obtained by admixture, shaping, drying and firing of an alumina binding agent and an alumina charge. The manufacture of the catalyst is characterised in that at least a portion of the active phase is introduced during the manufacture of the carrier, so that said active phase is to be found in a major part in the binding agent or in a major part in the charge or 65 both in the charge and in the binding agent before or during the admixture of the charge with the binding

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agent. The method comprises, for example, introducing at least a portion of the active phase, mostly with the binding agent or mostly with the charge during admixture of the charge with the binding agent.

According to an alternative embodiment of the process, the alumina charge (e.g. to improve thermal stability) may be at least partially replaced with an oxide selected from oxides of magnesium, calcium, 5 strontium, barium, scandium, yttrium, the lanthanides, gallium, indium, thallium, boron, silicon, titanium, zicronium, hafnium, thorium, germanium, tin, lead, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, rhenium, iron, cobalt, nickel, copper, zinc or bismuth.

The invention is concerned with catalytic reforming processes as well as catalytic processes for manufacturing aromatic hydrocarbons, said processes being conducted, for example, at a temperature of 10 430-600°C under an absolute pressure of 0.1-5 MPa with an hourly rate of 0.1-10 volumes of fluid charge per volume of catalyst, the molar ratio hydrogen/hydrocarbons being 1-20.

The catalysts used in these reactions comprise a carrier, generally alumina with a so-called active phase based on at least one metal and usually two metals or more.

Thus, specific catalysts suitable for the above-mentioned processes, are catalyst containing an alumina 15 carrier and suitable amounts of various metal elements (metals or metal compounds). Thus, specific examples of catalysts are those which generally contain the following additive proportions by weight with respect to the alumina carrier:

a) 0.05 - 2% of at least one precious metal selected from platinum, palladium, iridium, ruthenium, rhodium and osmium (preferably platinum, iridium, ruthenium and rhodium) or 0.1 - 30% of at least one metal

20 selected from iron, cobalt and nickel;

b) optionally 0.01 - 25% of at least one second metal selected for example, from titanium, rhenium, tin, germanium, indium, thallium, manganese, copper, silver, gold, niobium, lanthanum, cerium, samarium and other metals of the rare-earth family, zirconium, thorium, hafnium, lead, gallium, vanadium, uranium, chromium, molybdenum, tungsten, zinc, cadmium, bismuth, antimony and the like, and

25 c) optionally, for certain reactions, 0.1-10% of halogen, for example, chlorine or fluorine.

Such catalysts, largely used in the prior art, have been progressively improved by using a specific metal promoter at a particular critical concentration and have often resulted in remarkable results in the above reactions, as far as yields and reaction selectivity, as well as stability, and hence the life-time of the catalyst, are concerned.

30 It has now been observed that with a similar catalyst (i.e. a catalyst containing an alumina carrier and identical contents of active metals) the yield and the selectivity of the reaction for which it is used, as well as the stability and the life-time of the catalyst, may be increased. These improvements result from the particular method of catalyst manufacture according to the invention. Thus, for example, in reforming reactions, a yield improvement of only 0.1% by weight, would result insubstantial gain of gasoline, which 35 may be determined as follows:

An industrial unit of average size operating with a VVH of 1.65 (naphtha volume/catalyst volume/hour) requires about 50 tonnes of catalyst. This means that the unit is operated with:

40 x 1.65 = 66 tonnes of charge per hour,

40 i.e. 66 x 24 = 1 584 tonnes of charge per day,

i.e. 1 584x365 = 578 160 tonne of charge per year.

A yield by weight of 75% would result in an annual production of:

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45 578160 x "Yoo"= 620 tonnes of gasoline.

A mere increase of only 0.1% of the yield would result in an annual production of:

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578160 x"7pjjr= 434198.16tonnes of gasoline.

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This yield increase, although of relatively small amount would hence result in an annual gain of 434 198.16 - 433 620 = 578.16 tonnes of gasoline (i.e. 770.881 of charge corresponding to more than 30001 of crude oil). This is far from being negligible; thus showing the interest of any new method of catalyst manufacture.

The particular method of catalyst manufacture also provides catalyst which can be used in severe 55 operating conditions. Thus, more particularly, the use of catalysts prepared in conformity with the present invention is particularly adapted to reforming reactions to obtain a gasoline of octane number of at least 100, for example, or to obtain aromatic hydrocarbons. The severe conditions of catalytic hydroreforming reactions are more particularly the following: average temperature of about 480-580°C, pressure of about 0.5 -1.8 MPa (5-18 kg/cm2) preferably 0.6-1.3 MPa, hourly rate of 1-10 volumes of fluid charge per volume of 60 catalyst and recycle rate of 4-10 moles of hydrogen per mole of charge. The charge is generally a naphtha distilling between about 60 and about 200°C, particularly a straight-run naphtha.

Preferred catalysts according to the invention are particularly those cotaining:

- platinum,

- platinum and iridium,

65 - platinum and at least one metal selected from titanium, rhenium, tin, germanium, indium, thallium.

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manganese, nickel, iron, cobalt, zinc, copper, gold, silver, niobium, lanthanum, cerium, samarium,

zirconium, thorium, hafnium, lead, gallium, vanadium, technetium, uranium and selenium.

- platinum, iridium and tin,

- platinum, iridium and selenium,

5 - platinum, iridium and germanium, 5

- platinum, iridium and thallium,

- platinum, iridium and indium,

- platinum, iridium and titanium,

- platinum, iridium and rhenium,

10 - platinum, iridium and manganese, 10

- platinum, iridium, copper, gold or silver

- platinum, rhenium and at least one of the above-listed metals,

- platinum, germanium and at least one of the above-listed metals,

- platinum, tin and at least one of the above-listed metals,

15 - platinum, indium orthallium and at least one of the above-listed metals. 15

According to the invention, the alumina binding agent is preferably present as a powder.

The alumina binding agent should generally be gelable or coagulable by thermal or chemical action. ,

Gelation or coagulation by thermal action is well known in the art and may be obtained by evaporation of water from an aqueous suspension or dispersion of alumina forming the binding agent. Gelation or 20 coagulation by chemical action is also well known in the art and may be obtained by increasing the pH of an 20 aqueous suspension or dispersion of the alumina forming the binding agent, to more than 9, which corresponds to the isoelectric point of alumina.

Alimina binding agents used according to the invention are, for example, aqueous suspensions or dispersions of fine or ultra-fine boehmites having particles sizes within the colloidal range, i.e. lower than 25 about 2000 A. 25

Aqueous dispersions or suspensions of fine or ultra-fine boehmites may be obtained, as well known in the art, by peptization of these products in water or acidified water. The fine or ultra-fine boehmites used according to the invention may particularly be obtained by the process disclosed in French Patents Nos. 1 262 182 and 1 381 282 or in the European Patent Application No. 15 196.

30 French Patent No. 1 262 282 discloses a process for manufacturing fine or ultra-fine boehmite by heating 30 an aqueous alumina dispersion of the presence of a monovalent acid radical, the aqueous alumina dispersion being obtained from basic aluminium chloride, basic aluminium nitrate, aluminium hydroxide,

alumina gel or colloidal solutions. This product, sold on the market by Du Pont de Nemours, underTrade Mark Baymal, is a fine or ultra-fine fibrillar boehmite of 250 - 350 m2/g specific surface area.

35 French Patent No. 1 381 282 discloses a process for manufacturing fine or ultra-fine boehmite by 35

subjecting a suspension or cake of amorphous hydrated alumina gel, containing up to 35% by weight of alumina as Al203, and from 0.05 to 0.5 monovalent acid ions per mole of Al203of said alumina to a temperature of from 60 - 150°Cfor 15 hours to 10 days. The cake was obtained by drying, washing and filtering the alumina gel, continuously precipitated at a pH from 8 to 9 from a solution of sodium hydroxide 40 aluminate and nitric acid. The specific surface area of these products generally ranges from 200 to 600 m2/g. 40

European Patent Application No. 15 196 discloses a process for manufacturing boehmite, at least partially as ultra-fine boehmite, by treating in an aqueous medium of pH lower than 9, an active alumina powder obtained by rapid dehydration of hydrargillite in a hot gas stream.

As binding agent for alumina, aqueous suspensions or dispersions obtained from pseudo-boehmite, 45 amorphous alumina gels, aluminium hydroxide gels or ultra-fine hydrargillite, may be used. The 45

pseudo-boehmite may be prepared according to the process disclosed in US Patent 3 360 670 by reacting an alkaline aluminate solution with a solution of an inorganic acid. It may also be prepared, as disclosed in French Patent No. 1357 830, by precipitation at pH 9 at a temperature slightly higher than room temperature,

from reactants at such concentrations that about 50 g/l of alumina are obtained in the dispersion.

50 Amorphous alumina gels may be prepared according to the processes disclosed in "Alcoa paper" No. 19 50 (1972) - pages 9-12 and particularly by reacting an aluminate with acid, an aluminium salt with a base or an aluminate with an aluminium salt, by hydrolysis of basic aluminium salts or of aluminium alcoholate obtained by reacting aluminium with an alcohol.

Aluminium hydroxide gels may be those prepared according to US Patents Nos. 3 268 295 and 3 245 919. 55 Ultra-fine hydrargillite may be prepared according to the process disclosed in French Patent 1 373 808, by 55 subjecting alumina gels, as cakes containing 0.10 monovalent acid ions per molecule of Al203 of alumina, to a temperature of from room temperature to 60°C.

According to an alternative embodiment of the process of the invention, the alumina binding agent may at least be partially replaced with a silica suspension or dispersion having the same characteristics as the 60 alumina binding agent. 60

According to the invention, the alumina charge generally commprises a non-dispersable alumina portion optionally with a minor portion of dispersable alumina, which is dispersed in the composition, the non-dispersable portion amounting to at least 90% by weight of the charge. It may be preferable that the particle size of the non-dispersed portion of the composition is such that the average diameter of the alumina 65 particles of which it is formed, is 1-15 microns. 65

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The alumina charge may be any alumina compound having the above-stated characteristics, particularly hydrated alumina compounds such as: hydragillite, bayerite, boehmite, pseudo-boehmite and amorphous or substantially amorphous alumina gels, optionally in the dehydrated or partially dehydrated form of these compounds, which consist of transition aluminas and comprise at least one of the phases selected from rho, 5 chi, eta, gamma, kappa, theta, delta and alpha aluminas.

In particular, convenient alumina charges will be those obtained by one of the following processes, optionally after crushing and screening of the particles:

-An aqueous solution of an aluminium salt is precipitated with a solution of alkaline aluminate. The precipitate obtained is atomized and then suspended again in an aqueous solution of pH 4.5 to 7. The 10 resultant alumina mixture is atomized and dried; then the obtained product is washed, dried and fired (Process disclosed in US Patent 3 520 654).

-An alumina gel is precipitated at a pH of from 7.5 to 11, then washed, dried, again suspended and the product is quickly dehydrated in a hot gas stream at an inlet temperature of 350- 1000°Cand then fired (Process disclosed in French Patent 2 221 405).

15 -An alumina gel is precipitated at a pH of from 7 to 10.5, the precipitate is aged at a pH of from 10 to 11, the mixture obtained is homogenized and atomized at250-550°C and then fired (Process disclosed in British Patent 888 772).

-An alkaline aluminate is precipitated with an inorganic acid at a temperature of from 30 to 75°C. The resultant mixture is aged in a second reactor at 35-70°C, at a pH close to 7, recycled to the mixing reactor, and 20 the product is filtered, washed, dried by atomization and fired (Process disclosed in U.S. Patent 3 630 670.)

-Aluminium hydroxides or oxyhydroxides and more particularly hydrargillite, are rapidly dehydrated in a stream of hot gases. This dehydration is performed in any convenient apparatus by a hot gas stream, the inlet temperature of the gases in the apparatus generally varying from 400 to about 1200°C, and the contact time of the hydroxide oroxyhydroxide with the hot gases being generally from a fraction of second to 4-5 25 seconds. Such a process of manufacturing active alumina powder has been disclosed particularly in French Patent No. 1 108011.

- An active alumina powder obtained by quick dehydration of hydrargillite in a stream of hot gases, drying by atomization and then firing, is treated in an aqueous medium of pH lowerthan 9 (Process disclosed in the European Patent Application No. 15 196).

30 The alumina charges obtained according to the various processes may be classified into two groups. The first group concerns charges obtained after drying and optionally firing, which have a certain dispersion ratio.

These products may be used without further processing for the charge, optionally after crushing and screening. The second group concerns charges obtained after drying, which have a dispersion ratio lower 35 than that of the charges of the first group. These charges need, before use, to be fired at a temperature higherthan 300°C, optionally after crushing and screening.

In the process of the invention, the binding agent and/or the alumina charge may be at least partially replaced with an oxide selected from at least one of the metals, above called promoters, or additional metals.

The charge and the binding agent may be admixed as powders. The powdered binding agent may consist 40 of various products: boehmite, pseudo-boehmite, bayerite, amorphous alumina gels, aluminium hydroxide gels, ultra-fine hydrargillite in non-peptized state. The powder mixture is then contacted with water or acidified water. The charge-binding agent-water mixture is prepared so that the pH of the final composition is lowerthan 4, in such proportions that the dispersion ratio of the final composition is from 10 to 60%.

According to another method, the powdered charge and the binding agent, as an alumina suspension or 45 dispersion, may be admixed, with stirring, in such proportions that the dispersion ratio of the composition is from 10 to 60% and the pH of the final composition is lowerthan 4.

The present invention is thus concerned with the use of a catalyst whose manufacture is characterized in that at least a portion of the active phase, or a precursor thereof, is introduced during the shaping of the carrier, i.e. during the admixture of the binding agent with the charge. The active phase generally comprises 50 at least one metal from Group VIII, generally present in the catalyst as a metal perse, particularly when the catalyst is a noble metal of the platinum group, and optionally at least one other metal, generally as an oxide or sulfide, to promote the activity of the first metal. At least a portion of the active phase, as explained more in detail hereinafter, will be introduced either with the binding agent of the carrier or with the charge of the carrier or both with the charge and the binding agent. When the whole active phase is not introduced during 55 the manufacture of the carrier, the remaining portion of the active phase will be introduced later, as in conventional methods.

More particularly, at least the portion of the active phase, or its precursor, is introduced (a) either with the charge ((3) or with the binding agent, (7) or both with the charge and the binding agent.

Said portion of active phase may be added to the binding agent and/orto the charge during the mixture of 60 the charge with the binding agent.

With respect to the addition of a major part of the active phase itself to the binding agent, the operation may be performed:

(1) Either by impregnation of the binding agent in a conventional way (dry or wet) by means of an acidified aqueous solution of a metal salt or compound or of at least one metal of the active phase.

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For example, one method comprises impregnating the carrier with solutions of compounds of the metals to be introduced. Either a single solution of these metals or separate solutions for each metal or each group of metals may be used.

Examples of metal compounds, other than those of the noble metals from Group VIII (platinum family), are 5 for example the nitrates, chlorides, bromides, fluorides, sulfates or acetates of the metals or any other salt or oxide of these metals soluble in water or hydrochloric acid (e.g. chloroplatinate). Also organic complexes containing these metals may be convenient.

The noble metals from Group VIII and particularly platinum may be used in any known form, for example, for platinum, hexachloroplatinic acid, ammonium chloroplatinate, platinum sulfide, sulfate or chloride. 10 Ruthenium, for example, may be used in any known form, for example as its chloride, bromide, sulfate or sulfide or, for example, as its acetylacetonate and the like.

The halogen, when present in the catalyst, may originate from one of the above-mentioned halides or may be introduced as hydrochloric or hydrofluoric acid, ammonium chloride, ammonium fluoride, chlorine gas or hydrocarbon halide, e.g. CCI4, CH Cl3 or CH3CI.

15 A first method of manufacture comprises for example impregnating the binding agent or the charge of the carrier with an aqueous solution of a nitrate or other compound of a metal other than those from Group VIII, then a second impregnation is performed with a solution containing at least one Group VIII metal, (for example a solution of hexachloroplatinic acid, when using platinum).

Another method comprises impregnating the carrier with a solution containing together:

20 a) one or more metals from the Group VIII family (e.g. hexachloroplatinic acid),

0) one or more metals other than those from Group VIII (e.g. a chloride, bromide, fluoride, sulfate or acetate of the selected metal or any other salt of the selected metal soluble in water or in hydrochloric acid or in any other suitable solvent e.g. chloroplatinate or acetylacetonate and y) optionally chlorine or fluorine.

25 A further method comprises introducing the metal elements in as many successive impregnations as metal elements to be introduced in the catalyst; for example successively:

-a metal from Group VIII, by means of a solution containing the same,

- one or more metals from Group VIII (when the catalyst comprises several metals) by means of a solution containing the same, and 30 - finally the one or more other additional metals.

Of course, the order of the above-mentioned impregnations does not need to be as above stated and may be different;

(2) or by co-gelation of the alumina powderforming the binding agent with the active phase introduced as a colloidal suspension;

35 (3) or during the manufacture of the binding agent by co-precipitation of an alumina salt with a salt of the active phase. The binding agent is advantageously dried at a temperature lowerthan 300°C.

The addition of the active phase during admixture of the charge with the binding agent, preferably with introduction of the active phase in the binding agent or in the charge, maybe effected:

a) in several steps, or 40 b) in a single step.

(a) In several steps

When it is desired to introduce the active phase preferentially into the binding agent, the method comprises first introducing the binding agent in an aqueous solution, then a salt of the metal of the active phase and then the charge, previously saturated with a suitable salt, so that the salt of the active phase does 45 not penetrate into the charge (the salt to thus block the charge may be, for example, a volatile salt such as a nitrate, chloride, sulfate, ammonium salt, amine, hydroxylamine, hydroxylamine chloride, ammonium acetate and the like).

When it is desired to introduce the active phase preferentially into the charge, the method comprises introducing the charge, then the one or more salts of the metal of the active phase, and then the binding 50 agent blocked by a salt as above described.

(b) In a single step

In order to preferentially introduce the active phase into the binding agent or into the charge, either the charge or the binding agent is blocked as above indicated with a convenient salt, the active phase being thus fixed either in the binding agent, when the charge is blocked, or in the charge, when the binding agent is 55 blocked.

For introducing the active phase into the binding agent, the latter may preferentially have a specific surface area of about 150-600 m2/g and the charge any specific surface area but generally so selected that the ratio of the respective specific surface areas of the binding agent and the charge is higher than about 1.5. Thus the salt of the active phase is preferably fixed onto the binding agent.

60 Conversely, for introducing the active phase into the charge, the latter may preferentially have a specific surface area of about 100-600 m2/g, in the binding agent conveniently having such a specific surface area that the ratio of the respective specific surface areas of the charge and of the binding agent is higher than about 1.5.

When the active phase comprises more than one metal, it is possible to introduce separately each metal in 65 the binding agent or in the charge by anyone of the above described methods.

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Simultaneously with the introduction, in one or more steps, of at least a portion of the active phase, the binding agent and the charge may be shaped by any convenient means such as for example:

a) by extrusion,

b) by the so-called method of bowl granulation (or revolving bowl or revolving granulator and the like), or 5 c) by the so-called oil-drop method (drop falling into oil).

Any remaining portion of active phase may be added to the catalyst mass after shaping of the carrier.

Generally, it has been observed that the introduction into the charge of the active phase, or of a part thereof, imparts improved catalytic properties (selectivity, yield) to the final catalyst, and it has been observed that the introduction of the active phase or a portion thereof into the binding agent, imparts to the 10 final catalyst a higher mechanical strength (particularly desirable for use in moving bed applications) and hence a longer lifetime.

Thus, according to the invention, the catalyst alumina carrier to which the active phase, consisting for example of at least one metal from Group Vlll of the Periodic Table (e.g. cobalt, iron, nickel or a noble metal of the platinum family) is added, is preferably prepared by an extrusion method, by the so-called method of 15 bowl granulation or of revolving granulation (or an equivalent method such as that of the revolving bowl, and the like), or by the so-called oil-drop method, the method of manufacture being characterized in that at least a portion of the active phase is added eitherwith the charge or with the binding agent or both with the charge and the binding agent.

Generally, the active phase contains at least one metal from Group Vlll and at least one metal promoter. 20 Thus three preferred methods may be considered for shaping the binding agent and/or the charge and the portion of active phase during the manufacture of the carrier, depending on whether said active phase part is the Group Vlll metal and/or the metal promoter.

Hereinafter, the terms "major part of the oxide" of the promoter (or of the promoter oxides, when several promoters are used) or "major part of the Group Vlll metal" (or Group Vlll metals when several metals are 25 present in the catalyst) will be used. By "major part" is meant at least about 55% by weight of the total amount of oxide (or oxides, when several oxides are involved), or 55% by weight of the totality of the Group Vlll metal, expressed as metal (or Group Vlll metals when several metals are involved), present in the final catalyst, i.e. in the catalyst ready for use.

It will be appreciated that if all the desired metal oxide(s) promoters and/or if all the metal or metals from 30 Group Vlll have not been introduced by the indicated method, the oxide(s) promoter(s) and/or the metals from Group Vlll, not introduced by the indicated method may be introduced in the charge or at a later stage (e.g. after the manufacture of the carrier).

Forthe shaping of the carrier various techniques are possible.

I. In the oil-drop method of shaping the charge binding agent mixture, the metal from Group Vlll may be 35 introduced into the charge or into the binding agent but it is also possible to add it at a later stage (e.g. during the manufacture of the carrier, admixed with a portion of the active phase, in conformity with the invention) by any adequate conventional method, for example by impregnation. The promoter or additional metal, generally introduced as an oxide, may be added either to the binding agent or to the charge, or both to the binding agent and to the charge, or also, but generally in minor part, at the end of the carrier-active phase 40 admixture, by any method, for example by impregnation.

Six operating methods (1 to 6) are preferred:

Method 1: The major part of the metal oxide(s) promoter(s) is introduced with the binding agent and at least a portion, for example the major part, of the Group Vlll metal(s) is introduced with the binding agent.

Method2: The major part of the metal oxide(s) promoter(s) is introduced with the charge and at least a 45 portion, for example the major part, of the Group Vlll metal(s) is introduced into the binding agent.

It should be noted that any metal oxide(s) promoter(s) and/or Group Vlll metal(s) not introduced as above indicated may be introduced into the binding agent and/or the charge respectively or after the manufacture of the carrier. This not only applies to Methods 1 and 2 but also for Methods 3 to 6 below. It will be readily appreciated that when a minor portion of the oxide(s) promoter(s) and/or Group Vlll metal(s) is not 50 introduced in conformity with the indicated method, this or these minor portions may then be introduced in any other way.

Method 3\ The major part of the metal oxide(s) promoter(s) is introduced into the binding agent and at least a part, for example the major part, of the Group Vlll metal(s) is introduced into the charge.

Method 4\ The major part of the oxide(s) promoter(s) is introduced into the charge and at least a part, for 55 example the major part, of the Group Vlll metal(s) is introduced into the charge.

Method 5: The major part of the oxide(s) promoter(s) is introduced into the binding agent and the Group Vlll metal(s) are introduced at a later stage, afterthe manufacture of the carrier, for example by conventional impregnation.

Method 6: The major part of the oxide(s) promoter(s) is introduced into the charge and the Group Vlll 60 metal(s) are subsequently introduced afterthe manufacture of the carrier, for example by conventional impregnation.

II. When admixture is achieved by the revolving bolus granulatortype method, two methods (Nos 7 and 8) are generally selected for introducing at least part of the active phase into the carrier, particularly when the catalyst contains a Group Vlll metal as promoter.

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Afirst method (No. 7) comprises introducing the major part of the metal oxide(s) promoter(s) into the binding agent. A second method (No. 8) comprises introducing at last a part, for example the major part, of the metal oxide(s) promoter(s) into the charge. For these two methods, the total amount of the Group Vlll metal(s) is preferably introduced subsequently, afterthe preparation of the carrier, for example by 5 impregnation.

III. When the carrier active phase mixture is obtained by an extrusion type method, several methods are possible which correspond to the six methods 1 to 6 described above for the oil drop technique.

In the oil drop method, drops of binding agent and charge are introduced into a liquid immiscible with water in such a manner that the drops form substantially spherical particles. These particles are 10 simultaneously coagulated and/or subsequently made spherical with a gelling agent which removes stabilizing ligands. Also simultaneously, at least a portion of the active phase of the catalyst is added, either in the binding agent or in the charge or both in the charge and in the binding agent.

The liquid immisicible with water may be such that the drops fall (where the density of the liquid is lower than the density of the drops) or rise (where the density of the liquid is higher than the density of the drops). 15 Examples of such liquids which may be used in the process of the invention include crude oil, kerosene, dodecylbenzene,trichloroethylene and perchloroethylene, as well as organic solvents, hydrocarbons and inorganic oils generally.

The gelling agent which removes stabilizing ligands may for example be ammonia, an ammonia solution, ammonium carbonate, long-chain amines (particularly those sold undertrade mark "Primene"), hex-20 amethylenetetramine and urea.

The resultant drops may be recovered from the medium used for their shaping and/or coagulation.

According to a peferred embodiment, the drops of the mixture are introduced into a column containing an upper phase comprising crude oil and a lower aqueous phase comprising an ammonia solution. Shaping takes place in the upper phase and gelation essentially in the lower phase. The temperature of the crude oil is 25 generally close to room temperature. The pH of the ammonia solution should be maintained above 9. The residence time of the drops in the ammonia solution is a few minutes and generally less than about 15 minutes. In these conditions, the recovered balls are sufficiently hard and are not deformed by subsequent handling. Two new advantages of the process of the invention appear particularly for the step of spheroidal shaping and gelation: the shaping is performed at room temperature and the gelation is performed very 30 quickly, thus it is not absolutely necessary to proceed to a subsequent ageing of the balls in a basic solution, the latter having a sufficient strength, after a short residence time in the ammonia phase.

According to a second process, the drops of the mixture are introduced (suspended) in a water immiscible liquid, liable to remove water from the drops. This immiscible liquid extracts water from the drops and causes their gelation in a spheroidal shape. For example, 2-ethyl-1-hexanol or a long-chain aliphatic alcohol, 35 sold undertrade markOctylol, may be used.

According to a third process, the mixture is admixed with at least one water-soluble monomer whose non cross-linked polymer is soluble in water orforms a gel. The resultant mixture is then dispersed, as drops, in a hot fluid medium where substantial polymerization of the monomer occurs. The monomer may be an acrylic compound of general formula:

40

/

CH2 = c (Rt) — C

45

wherein is H or methyl, R2 is OR3 or NR3R4, in which R3 and R4 represent H or a hydrophilic radical, particularly a hydroalkyl radical containing 1 or 2 carbon atoms, or a methoxymethyl radical. The main steps of the process are described in French Patents No. 2 261 056 and 2 261 057.

50 However prepared, the balls are then separated from the gelation medium and dried and fired at a temperature of about 550-1100°C.

The resulting balls have a total pore volume of 0.30-1.7 cc/g, the micropore volume (i.e. of pores of diameter lowerthan 0.06 micron) being 0.5-1 cc/g, and the macropore volume (i.e. of pores of diameter larger than 0.06 micron) being 0.05-0.7 cc/g. The average diameter of the macropores is generally 0.1-10 micron. 55 The specific surface area of the balls is about 80-350 m2/g (BET method, products dried at 110°C), and their breaking strength is higher than 1 kg.

In the extrusion method orthe revolving granulator method the manufacture of the catalyst is carried out as follows:

1) in an optional first step, the carrier material is washed;

60 2) in a second step, the carrier material is dried by any appropriate method, for example by oven-drying, to obtain a powder which has the same structure as the starting material and which, after drying, is characterized by a loss on heating of about 15-40% at 1000°C;

3) in an optional third step, the material is washed and dried;

4) at this stage, before the subsequent steps, it is often preferably to fire at least partially the dried powder.

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GB 2 150 853 A

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Thus, 20-80% of the alumina powder may be subjected to a temperature of about 200-800°C and the fired powder can be admixed with non fired powder. Here the object is to impart to the final product a macro-porosity by means of two-phase products. More particularly it is desired in this case to obtain, after admixture of the fired powder with non-fired powder, a powder of particle size ranging from 1 to 50 microns 5 and having a critical macro-porosity corresponding to pores of a diameter larger than about 600 A; and 5

5) the resultant powder is then shaped:

(a) either by extrusion, (b) or by means of a revolving bolus-granulator or by any equivalent means, this shaping being characterized by the simultaneous addition of at least a portion of the active phase into the binding agent (dispersed alumina) or into the charge (non-dispersed alumina).

10 The extrusion operation is as follows:- 10

For a period from 5 minutes to 5 hours, the powder is mixed in the presence of water or acidified water, the water or acidified water containing at least a portion of the catalyst active phase (i.e. metal oxides and/or precious metals).

The amount of water or of acidified water is generally 50-89% by weight of the powder weight. 15 The resultant paste is extruded by any convenient method, for example with a single-screw or 15

double-screw extruding machine or any other machine, through a drawing plate.

The resultant extrudates may be dried at a temperature generally lower than 350°C so that the loss on heating of the resultant solids is about 15-40%.

At this stage, the portion of active phase not yet admixed to the carrier may be optionally and 20 conventionally introduced and the operation terminates with a drying, for example at a temperature lower 20 than 350°C.

Then optionally, the extrudates are subjected to a hydrothermal treatment in a neutral, acid or basic medium at a temperature of 80-500°C, so that the amorphous structures change to boehmite or pseudo-boehmite structures and lead to improved mechanical properties.

25 The obtained extrudates may be fired at a temperature generally from 350 to 1000°C. 25

The sequential order of these two latter steps may be reversed.

When operating according to the revolving granulator method or similar (bowl granulator or other:

revolving plate, rotary bowl, etc...), the operation is conducted as follows: on the one hand, the powder is caused to run onto the granulator and, on the other hand, an aqueous solution or an acidified aqueous 30 solution is simultaneously introduced by pouring or by pulverization, onto the granulator. This solution 30

contains at least a part of the active phase of the catalyst (i.e. metal oxides and/or precious metals).

Generally, the bowl granulator or the granulator is wet while the powder rotates. The powder agglomerates by sticking of the powder particles present. The particles are removed according to usual methods, for example by ejection from the granulator by centrifugation and then they are dried and fired as 35 above-explained for the extrusion method (with optional introduction, as above explained, of the portion of 35 active phase not yet introduced on the carrier).

An alternative in the method would consist of feeding the granulator with a portion of powder (about 0-40% thereof) already diluted with the aqueous solution or preferably with the acidified aqueous solution. (It is so possible to dilute a portion of the powder in the acid which is used to form said acidified aqueous 40 solution). 40

The following non-limiting Examples illustrate the invention:-

Example 1

Several catalysts with an alumina base, containing platinum and/or various additional metals, are 45 prepared and subsequently tested for their utility in reforming reactions. 45

Six catalysts are prepared according to the following methods: Catalysts A1f B1r Ci, D1f E-i, and F-i (not conforming with the invention).

Catalysts At to F-, contain by weight 0.2 % platinum and 1.18% chlorine and further contain :

50 For catalyst An : 0.5% rhenium 50

For catalyst B-i : 0.5% tin

For catalyst C-i : 0.5% thallium

For catalyst D-i : 0.5% indium

For catalyst E-i : 0.5% titanium

55 For catalyst F-i : 0.5% iridium 55

Catalyst At is prepared by adding to 100 grams of 7 alumina (specific surface : 280 m2/g):

-on the one hand, 65 cc of an aqueous solution containing:

1.90 g of concentrated hydrochloric acid (density 1.19)

60 10 g of an aqueous solution of chloroplatinicacid of 2% platinum content by weight, 60

- on the other hand, 51 cc of a perrhenic acid solution at 0.98 % by weight rhenium content.

The contact is maintained for 10 hours and then drying is performed at 100°Cin a stove, for 6 hours; then calcination is conducted in a dry air stream for 2 hours at 380°C and then for 2 hours at 530°C. Reduction is effected in a dry hydrogen stream (activated alumina) for 2 hours at 450°C.

9

GB 2 150 853 A

9

Catalysts Ci, D1f E^ and F, have been prepared by adding to 100 g of alumina :

- on the one hand, 65 cc of an aqueous solution containing:

1.90 g of concentrated hydrochloric acid (density 1.19) and

10 g of an aqueous solution of chloroplatinic acid having 2 % by weight platinum content, and 5 -on the other hand, 100 cc of an aqueous solution containing:

2.5 g of a 20 % tin acetate solution for catalyst B-,,

2.5 g of thallium acetate solution having a 20% by weight thallium content for catalyst C1(

10.75 g of titanium trichloride solution containing 15% by weight of titanium chloride for catalyst E1( 1.87 g of indium nitrate for catalyst D1( and 10 1.74ccof a 2.3 % by weight aqueous solution of chloroiridic acid, for catalyst F-i.

The obtained catalysts are dried, calcined and reduced as indicated for catalyst Ai.

These catalysts have a specific surface of 270 m2/g.

Catalysts A2 to F2 (not conforming with the invention)

15 An ultra-fine boehmite sol is prepared as follows:

A cake of alumina gel is prepared by continuous precipitation of a sodium aluminate solution whose Al203/Na20 ratio by weight is about 1.08, at a concentration of 100 g/l, expressed as Al203, with a nitric acid solution at such a concentration that the suspension contains about 50 g/l of alumina, expressed as Al203, and the N03/Al203 molecular ratio is 0.16. The precipitation pH is then about 9. The so-prepared gel cake is 20 dried, filtered and washed. It is then treated for 24 hours at 115°C in a shaked autoclave. The resultant product is a paste containing 12 % of alumina, expressed as Al203.

The specific surface, measured by the BET method, of said product, dried in a stove at 110°C, is about 300 m2/g. The geometrical surface of this product, measured after drying by dispersion in isopropanol, azeotropic distillation and then evaporation of isopropanol, is about 550 m2/g.

25 The photograph of this product, obtained with an electronic microscope, shows that it consists of ultra-fine boehmite, entirely fibrillar, composed of monocrystals shaped as elongate and very narrow lathes, often forming bundles, the microcrystals having a longitudinal size of about 500-1000 A. When considering the microcrystals as cylinders, it can be deduced from the specific surface, measured by the BET method, that these microcrystals have an average diameter of 55 A. The DebyeScherrer diagram of this product shows the 30 absence of reflections (hkl), a halo (012) and a clear reflection (200).

The resulant sol, which constitutes the binding agent, is contacted with an amount of acidulated water so selected that the pH of the final composition be lowerthan 4 and that the dispersion rate of the composition be 30 %. The binding agent is admixed with a y alumina charge, as powder. The amounts of binding agent and charge are so selected that the resultant carrier contains, by weight, 30 % of binding agent and 70 % of 35 charge. The charge-binding agent mixture is effected as follows:

Drops of the mixture of dispersed alumina (binding agent) and non dispersed alumina (charge) are formed by means of calibrated tubes of about 2.5 mm internal diameter. The drops fall into a column of 600 mm diameter, containing an oil layer of about 6 cm, floating above an ammonia solution at about 20 g/l concentration. The residence time of the particles in the ammonia solution is about 2 minutes. The drops 40 become round in the oil and gel in the ammonia solution. The recovered balls are very hard and undergo without deformation the transfer operations. They are then dried and calcined at 950°C for one hour. Their diameter is about 3.5 to 4 mm.

On the carrier so prepared by the oil-drop method, platinum and the additional metals are added according to the techniques indicated for catalysts Ai to F1r so as to obtain the same metal contents as in 45 catalyst A-i to F-i.

Catalysts A3 to F3 (conforming with the invention)

The manufacture of catalysts A2 to F2 is repeated but by adding the solution containing the additional metal (perrhenic acid or tin acetate or thallium acetate or titanium trichloride or indium nitrate), or 50 chloroiridic acid, at the beginning and then during operation by the oil-drop method, said solution being introduced in the binding agent (dispersed boehmite). Platinum is introduced subsequently, as for catalyst A2 to F2.

Catalysts A4 to F4 (not conforming with the invention)

55 A sol of ultra-fine boehmite is prepared according to the technique used for catalysts A2 to F2. The mixture of binding agent (dispersed boehmite) and charge (non dispersed boehmite) is extruded from its paste with water and nitric acid : thus, a homogeneous paste is prepared after admixture, for 3 hours, on the one hand, of 500 g of alumina and, on the other hand, of a solution containing 250 cc of distilled water and 20 cc of 0.001 M nitric acid.

60 The paste is extruded through a drawing plate of 1.5 mm, on an extruder of the piston type.

The extrudates are dried at300°C so that the loss on heating of the obtained solid is about 20 %.

To the resultant catalyst mass, platinum and additional metals are added according to the technique used for manufacturing catalysts A-i to Fn.

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GB 2 150 853 A

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Catalysts As to Fs (conforming with the invention)

The manufacture of catalysts A4 to F4 is repeated but with the addition of the solution containing the additional metal into the binding agent (dispersed boehmite) during the extrusion.

Platinum is added subsequently, as for catalysts A4 to F4.

5 5

Catalysts A6 to Fe (not conforming with the invention)

An ultra-fine boehmite sol is prepared according to thetechnique usedforthe preparation of the catalysts A2 to F2. The mixture of binding agent (dispersed boehmite) and charge (non dispersed boehmite) is agglomerated by means of a revolving granulator: 500 grams of powder are poured on the granulator and 10 simultaneously an aqueous solution containing 250 cc of distilled water and 20 cc of 0.001 M nitric acid is 10 introduced on the granulator.

The granulator or bowl granulator is thus wet as the powder rotates.

The powder agglomerates by sticking of the present powder particles.

The particles are removed by ejection from the bowl granulator by centrifugation and then dried at 300°C 15 so that the loss on heating of the obtained solids be about 20%. 15

To the resultant catalyst mass, platinum and additional metals are added according to the technique used for the preparation of catalysts An to F-,.

CatalystA7 to (conforming with the invention)

20 The manufacture of catalysts A6 to F6is repeated but with the addition of the additional metal solution to 20 the binding agent (dispersed boehmite), during the granulation step.

Platinum is added subsequently, as for catalyst A6 to F6.

Example 2

25 All the catalysts, before use, are reduced in the presence of hydrogen, as for catalysts Ai to Fi. 25

In view to obtain a gasoline having a clear octane number of 103, a naphtha is treated, whose characteristics are as follows :

ASTM distillation 80-160°C

30- composition: aromatic hydrocarbons 7% by weight 30

naphthenic hydrocarbons 27 % by weight paraffinic hydrocarbons 66 % by weight

"clear Research" octane number about 37.

average molecular weight 110

35 - density at 20°C 0.782 35

This naphtha passes, with recycle hydrogen, over catalysts At to F1f A2to F2, A3 to F3, A4to F4, A5to F5, A6 to F6, A7 to F7.

The operation is conducted continuously in a moving bed reactor. The operating conditions are as follows:

40 40

pressure 1 MPa temperature 530°C

molar ratio H2/hydrocarbons 8

naphtha volume/catalyst volume/hour 1.65

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GB 2 150 853 A

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Table I below indicates, after 200 hours, the C5 + yield and the hydrogen percentage contained in the recycled gas.

A significant gain of yield and of recycle hydrogen is obtained when the catalyst is prepared in conformity with the invention (catalysts A3 to F3, A5 to Fs and A7 to F7) with a preference for catalysts A3 to F3, prepared 5 by the so-called oil-drop method.

TABLE 1

Yield

Recycle gas

10

Catalyst

Precious metal

Promoter metal

Cs + (weight)

%h2

(molar)

ai

Platinum rhenium

74.9

75.3

a2

II

ii

75.0

75.3

15

a3

it ii

75.9

76.5

a4

//

"

74.9

75.4

a5

n ii

75.8

76.4

a6

it

"

75.0

75.2

a7

ii

"

75.7

76.2

20

BI

ii

Tin

76.6

76.1

b 2

ii il

76.6

76.1

b3

ii it

77.6

77.3

b4

it ii

76.5

76.1

b5

ii

"

77.5

77.2

25

b6

it il

76.5

76.1

b7

ii it

77.4

77.2

Ci it thallium

74.9

75.0

C2

it ii

74.9

75.1

c3

ii il

75.9

76.2

30

c4

ii ii

75.0

75.1

c5

ii il

75.8

76.1

c6

it ii

74.9

75.0

c7

ii il

75.7

76.0

di ii

Indium

75.6

75.1

35

d2

it

"

75.5

75.1

d3

n a

76.5

76.1

d4

it

"

75.5

75.2

d5

it

"

76.4

76

d6

it

»/

75.5

75.1

40

d7

11

a

76.2

75.9

ei

II

Titanium

76.6

76.2

e2

II

ii

76.7

76.2

e3

11

"

78.1

77.4

e4

II

li

76.7

76.2

45

e5

II

"

77.9

77.3

e6

II

II

76.6

76.1

e7

ii

"

77.8

77.2

f,

Platinium &

75.2

74.9

Iridium

50

f2

ii

75.3

75.0

f3

ii

76.5

76.0

f4

ii

75.2

74.9

f5

if

76.4

75.9

f6

n

75.3

74.9

55

f7

il

76.2

75.8

Example 3

Several catalysts with an alumina carrier are now prepared which all contain by weight: 0.2 % platinum,

0.04% iridium,

60 0.5% indium,

1.18 % chlorine.

Anyone of the above-mentioned techniques can be used.

Thus, a catalyst G, not conforming with the invention, is prepared by using the same technique as for the preparation of catalysts A2 to F2, i.e. they are prepared from an ultra-fine boehmite sol shaped by oil-drop, 65 the metals being subsequently introduced by conventional impregnation.

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12 GB 2 150 853 A

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A catalyst H is also prepared, as above, by introducing however indium in the binding agent, as for catalysts A3 to F3.

A catalyst I is also prepared by introducing the totality of the metals (indium, platinum and iridium) into the binding agent.

Finally, a catalyst J is prepared by introducing indium and one half of the chloroplatinicand chloroiridic acids solutions in the binding agent and the other half of said solutions subsequently, after shaping of the binding agent and the charge, by conventional impregnation.

The results, in the operating conditions of example 2, are given in Table II.

10

TABLE II

10

15

Catalyst

Precious metal

Platinium & Iridium

Promoter metal

Indium

Yield ofCs + (weight)

79.5

Gas recycle

%HZ

(molar)

79.1

15

20

Platinium & Iridium

Indium

80.4

79.9

20

Platinium & Iridium

Indium

80.6

80.2

25

Platinium & Iridium

Indium

80.9

80.6

25

Claims (1)

1. 30 1. A catalytic reforming or an aormatic hydrocarbons production process effected in the presence of a 30 catalyst comprising (a) a carrier comprising a major part of alumina and, (b) an active phase comprising at least one metal from Group Vlll of the Periodic Table and optionally at least one additional metal or promoter, wherein the carrier is obtained by admixing an alumina based binding agent with an alumina based charge, shaping, drying and optionally firing the resultant mixture, the proportion by weight of the

   35 binding agent amounting to 15-40% of the total carrier and the proportion by weight of the charge 35

   amounting to 60-85% of the total carrier, the alumina binding agent having a major proportion of dispersed alumina with optionally a minor proportion of non-dispersed alumina (the proportion of dispersed alumina being at least 70% by weight of said binding agent), the alumina charge having a major proportion of non-dispersed alumina with optionally a minor proportion of dispersed alumina (the proportion of dispersed

   40 alumina being less than 10%byweightof said charge),and the dispersion ratio of the composition resulting 40 from the mixture of the binding agent with the charge being from 10 to 60%, and wherein at least a proportion of the active phase or of a precursor therefor is introduced with the charge during the preparation of the carrier and/or with the binding agent during the process of admixing the binding agent with the charge.

   45 2. A process according to claim 1, wherein admixture of the binding agent with the charge is effected by 45 the oil-drop method, the extrusion method or the revolving bowl granulator method.

   3. A process according to either of claims 1 and 2, wherein at least said proportion of the active phase or precursor therefor is introduced during the admixture of the charge with the binding agent, in a major part with the binding agent or in a major part with the charge.

   50 4. A process according to any one of the preceding claims wherein at least a part of the active phase is 50 introduced with the binding agent during admixture of the charge with the binding agent by first introducing an aqueous solution of the binding agent, then a salt of the metal of the active phase and then the charge, the charge having been saturated with a further salt so that the salt of the active phase does not penetrate into the charge.

   55 5. A process according to any one of claims 1 to 3 wherein at least said part of the active phase is 55

   introduced with the charge during admixture of the charge with the binding agent by first introducing the charge in an aqueous solution, then a salt of the metal of the active phase and then the binding agent, the binding agent having been saturated with a further salt so that the salt of the active phase does not penetrate into the binding agent.

   60 6. A process according to any one of claims 1 to 3 wherein a part of the active phase, the binding agent 60 and the charge are introduced simultaneously and said part of the active phase is either introduced into the binding agent while blocking the charge with a salt, or introduced into the charge while blocking the binding agent with a suitable salt.

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   GB 2 150 853 A

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   7. A process according to any one of the preceding claims wherein the major part of the one or more additional metals is introduced into the binding agent and the major part of the one or more Group Vlll metals is introduced into the binding agent or into the charge.

   8. A process according to anyone of claims 1 to 6 wherein the major part of the one or more additional

   5 metals is introduced into the charge and the major part of the one or more Group Vlll metals is introduced 5 into the binding agent or into the charge.

   9. A process according to any one of claims 1 to 6 wherein the major part of the one or more additonal metals is introduced into the binding agent or into the charge and the major part of the one or more Group Vlll metals is introduced subsequently into the carrier.

   10 10. A process according to any one of the preceding claims substantially as herein described. 10

   11. A process according to any one of the preceding claims substantially as herein described in anyone of the Examples.

   12. A catalyst as defined in claim 1.

   13. A catalyst as defined in claim 1 substantially as herein described.

   15 14. A catalyst as defined in claim 1 substantially as herein described in any one of the Examples. 15

   15. Each and every novel product, process, method, apparatus and composition as herein disclosed.

   Printed in the UK for HMSO, D8818935, 5/85, 7102.

   Published by The Patent Office, 25 Southampton Buildings, London, WC2A 1AY, from which copies may be obtained.